JPH1033971A - Silicone resin hollow body and manufacture thereof - Google Patents
Silicone resin hollow body and manufacture thereofInfo
- Publication number
- JPH1033971A JPH1033971A JP8210520A JP21052096A JPH1033971A JP H1033971 A JPH1033971 A JP H1033971A JP 8210520 A JP8210520 A JP 8210520A JP 21052096 A JP21052096 A JP 21052096A JP H1033971 A JPH1033971 A JP H1033971A
- Authority
- JP
- Japan
- Prior art keywords
- silicone resin
- capsules
- water
- hollow body
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002775 capsule Substances 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims description 21
- 229920001169 thermoplastic Polymers 0.000 claims description 14
- 239000004416 thermosoftening plastic Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 18
- -1 polysiloxane Polymers 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 238000005507 spraying Methods 0.000 abstract description 6
- 229920001296 polysiloxane Polymers 0.000 abstract description 5
- 238000005187 foaming Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 125000003944 tolyl group Chemical group 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- KKHHHNGSTZPWLZ-UHFFFAOYSA-N 9,9-dimethyldecan-1-ol oxirane Chemical compound C1CO1.CC(CCCCCCCCO)(C)C KKHHHNGSTZPWLZ-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/043—Drying and spraying
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1372—Randomly noninterengaged or randomly contacting fibers, filaments, particles, or flakes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1386—Natural or synthetic rubber or rubber-like compound containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2984—Microcapsule with fluid core [includes liposome]
- Y10T428/2985—Solid-walled microcapsule from synthetic polymer
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、シリコーンレジン
中空体およびその製造方法に関する。The present invention relates to a hollow silicone resin body and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、シリコーンゴムやシリコーンレジ
ンは、耐熱性、耐候性、耐薬品性、電気絶縁性等の多く
の優れた特性を有するため各種の用途に使用されてい
る。これら優れた物理的、化学的性質を有するシリコー
ンゴム粒子やシリコーンレジン粒子はよく知られている
が、中空体については、紫外線硬化性液状オルガノポリ
シロキサン組成物に気体状物を混合し、この混合物を水
中に分散させて撹拌しながら紫外線を照射することによ
り、硬化させて固体オルガノポリシロキサン中空体（マ
イクロカプセル）としたものが特開昭５５−５７８７号
公報に示唆されているにすぎない。しかし、この公報に
は熱可塑性シリコーンレジン自体の中空体およびその製
法に関する記載も示唆もされていない。こうした硬化し
たオルガノポリシロキサン中空体（マイクロカプセル）
は、加熱したり溶媒に浸漬しても外殻が容易に破れない
という欠点があり、例えば、シリコーンゴムスポンジな
いしシリコーンゴムフォームの良好な発泡剤となり得な
いという欠点がある。2. Description of the Related Art Conventionally, silicone rubber and silicone resin have been used in various applications because they have many excellent properties such as heat resistance, weather resistance, chemical resistance and electrical insulation. Silicone rubber particles and silicone resin particles having excellent physical and chemical properties are well known, but for hollow bodies, a gaseous substance is mixed with an ultraviolet-curable liquid organopolysiloxane composition, and this mixture is mixed. Is dispersed in water and irradiated with ultraviolet rays with stirring to harden it to form a solid organopolysiloxane hollow body (microcapsule), which is merely suggested in JP-A-55-5787. However, this publication neither describes nor suggests a hollow body of the thermoplastic silicone resin itself and a method for producing the same. Such a cured organopolysiloxane hollow body (microcapsule)
Is disadvantageous in that the outer shell is not easily broken even when heated or immersed in a solvent. For example, it cannot be a good foaming agent for silicone rubber sponge or silicone rubber foam.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、加熱
すると外殻が破れてカプセル内の膨張した気体が発泡源
となりうるシリコーンレジン中空体とその製造方法を提
供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a silicone resin hollow body in which the outer shell is broken when heated and the expanded gas in the capsule can be a foaming source, and a method for producing the same.
【０００４】[0004]
【課題の解決手段】本発明は、熱可塑性シリコーンレジ
ンをカプセルの外殻とする平均粒径が０.１〜１００μ
ｍであるシリコーンレジン中空体、および溶媒に溶解し
た熱可塑性シリコーンレジンと水との分散液を熱気中に
噴霧し、該溶媒と水を揮発させると共に、噴霧状態で該
熱可塑性シリコーンレジンを中空粒子状に固化させるこ
とを特徴とする、熱可塑性シリコーンレジン中空体の製
造方法に関する。According to the present invention, a thermoplastic silicone resin having a capsule outer shell having an average particle size of 0.1 to 100 μm is provided.
m, and a dispersion of a thermoplastic silicone resin and water dissolved in a solvent is sprayed into hot air to volatilize the solvent and water, and the thermoplastic silicone resin is sprayed to form hollow particles. The present invention relates to a method for producing a thermoplastic silicone resin hollow body, characterized in that the hollow body is solidified.
【０００５】[0005]
【発明の実施の形態】本発明のシリコーンレジン中空体
は、カプセルの外殻が熱可塑性シリコーンレジンであ
り、カプセル内には空気，窒素ガス，ヘリウムガスのよ
うな気体が存在する。カプセルの外径は平均０.１〜１
００μｍであり、平均５〜５０μｍのものが製造容易で
ある。カプセルの外殻の厚さはカプセルの直径の１０％
前後が多い。形状は、特に限定されないが、球形のもの
が製造しやすい。かかるシリコーンレジン中空体のカプ
セルを形成するシリコーンレジンは、熱可塑性であり、
常温下では固体であるが、加熱すると軟化し、溶融す
る。中空体の製造のしやすさと用途面から軟化点が４０
〜２００℃範囲内にあることが好ましい。このシリコー
ンレジンは、好ましくは一般式：ＲａＳｉＯ
(4-a)/2（式中、Ｒは１価の置換または非置換の炭化水
素基で、ａは０.８〜１.８の数を示す）で表わされるオ
ルガノポリシロキサンであり、１価の置換または非置換
の炭化水素基としてはメチル基、エチル基、プロピル
基、ブチル基のようなアルキル基；フェニル基、トリル
基のようなアリール基；ビニル基、ヘキセニル基のよう
なアルケニル基；クロロフェニル基、３,３,３−トリフ
ルオロプロピル基のようなハロゲン化炭化水素基などが
例示されるが、入手のしやすさ、経済性、耐熱性などを
考慮すると、メチル基およびフェニル基が好ましい。こ
のシリコーンレジンとしては、ＲＳｉＯ3/2単位からな
るもの、ＲＳｉＯ3/2単位とＲ2ＳｉＯ2/2単位からなる
もの、Ｒ3ＳｉＯ1/ 2単位とＲＳｉＯ3/2単位とＲ2ＳｉＯ
2/2単位からなるもの、Ｒ3ＳｉＯ1/2単位とＳｉＯ4/2単
位からなるもの、Ｒ3ＳｉＯ1/2単位とＲ2ＳｉＯ2/2単位
とＳｉＯ4/2単位からなるものが例示される。このシリ
コーンレジンの分子中にシラノール基やメトキシ基，エ
トキシ基が微量ないし少量残存していてもよい。このシ
リコーンレジンの軟化点は４０℃〜２００℃である。軟
化点が４０℃より低いと、シリコーンレジン中空体の貯
蔵安定性が著しく低下し、また２００℃を超えると難溶
融となって、取扱いが困難となるからである。したがっ
て、好ましくは６０℃〜１８０℃である。ここで、軟化
点はレジンが自重または自身の表面張力で流動開始する
温度であり、この温度はレジン粒子を一定温度で加熱し
ながら顕微鏡により観察する方法によって容易に測定す
ることができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the silicone resin hollow body of the present invention, the outer shell of the capsule is a thermoplastic silicone resin, and a gas such as air, nitrogen gas and helium gas exists in the capsule. The average outer diameter of the capsule is 0.1 to 1
It is 00 μm, and an average of 5 μm to 50 μm is easy to manufacture. The outer shell thickness of the capsule is 10% of the capsule diameter
There are many before and after. The shape is not particularly limited, but a spherical shape is easy to manufacture. The silicone resin forming the capsule of such a silicone resin hollow body is thermoplastic,
It is solid at room temperature, but softens and melts when heated. The softening point is 40 from the viewpoint of ease of production of hollow body and application.
It is preferable that it is in the range of -200 ° C. The silicone resin preferably has the general formula: RaSiO
(4-a) / 2 (wherein R is a monovalent substituted or unsubstituted hydrocarbon group, and a is a number from 0.8 to 1.8), Examples of the divalent substituted or unsubstituted hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and hexenyl group. A halogenated hydrocarbon group such as a chlorophenyl group and a 3,3,3-trifluoropropyl group, and the like. However, in consideration of availability, economy, heat resistance, and the like, a methyl group and a phenyl group are considered. Is preferred. As the silicone resin, those comprising RSiO 3/2 units, those composed of RSiO 3/2 units and R 2 SiO 2/2 units, R 3 SiO 1/2 units and RSiO 3/2 units and R 2 SiO
2/2 units, R 3 SiO 1/2 units and SiO 4/2 units, R 3 SiO 1/2 units, R 2 SiO 2/2 units and SiO 4/2 units Is exemplified. A small or small amount of silanol group, methoxy group, or ethoxy group may remain in the molecule of the silicone resin. The softening point of this silicone resin is from 40C to 200C. If the softening point is lower than 40 ° C., the storage stability of the silicone resin hollow body is remarkably reduced. If the softening point is higher than 200 ° C., it becomes difficult to melt, and handling becomes difficult. Therefore, the temperature is preferably from 60C to 180C. Here, the softening point is a temperature at which the resin starts to flow under its own weight or its own surface tension, and this temperature can be easily measured by a method of observing with a microscope while heating the resin particles at a constant temperature.
【０００６】このようなシリコーンレジン中空体は、熱
可塑性シリコーンレジンを溶媒に溶解した溶液と水を機
械的に混合ないし攪拌して分散液を調製し、次に該分散
液を熱気流中に噴霧して該溶媒と水を揮発させると共に
噴霧状態でシリコーンレジンを中空粒子状に固化するこ
とによって容易に製造される。まず、熱可塑性シリコー
ンレジンを溶解する溶媒に溶解し、該シリコーンレジン
が均一な溶液を形成させるのであるが、ここで使用され
る溶媒は、熱気流中で揮発することが可能で水と非相溶
性・非混和性のものから選択すればよく、沸点が水より
低い３０〜９０℃の範囲内にあるものが望ましい。この
ような溶媒としてジクロルメタン，クロロホルム，１,
１−ジクロロエタン，１,１,１−トリクロロエタン，ア
セトン，メチルエチルケトン，ベンゼンが例示される。
次に、シリコーンレジン溶液と水とを混合ないし攪拌し
て分散液をつくる。そのためにはブレード形高速混練
機、例えば、ピンミキサ、タービュライザ、スピードミ
キサ、サターンミキサなどを使用することによって容易
に行うことができる。また、熱気流中への噴霧方法は、
溶液を微粒子状液滴として噴霧できる方法であればよ
く、特に限定されない。この噴霧方法としては、高速回
転ディスクに分散液を滴下して遠心力で微粒子化して噴
霧する方法、分散液を気体と共に噴射することによって
噴霧する方法、分散液を超音波で微粒子化して噴霧する
方法などが例示されるが、一般に２流体ノズルといわれ
ている噴霧ノズルを使用し、分散液を気体と共に噴霧
し、かつ、２方向から噴霧した微粒子を衝突させてより
細かい粒子にする方法が好ましい。噴霧温度と熱気流の
温度は通常室温から水の沸点温度以下、すなわち４０℃
〜９０℃の範囲内が望ましい。かくして熱気流中に噴霧
された微粒状液滴は、熱気流に乗って移動する間に溶媒
が揮発し、中空状のシリコーンレジン粒子、すなわち、
シリコーンレジン中空体となる。ここで、分散液噴霧後
捕集までの間に、溶媒の揮発と系外への放熱によって熱
気流温度は低下するが、捕集までの間に揮発した溶媒が
凝縮することがないように熱気流の吹き出し温度と気流
速度を調整する必要がある。なお、シリコーンレジン中
空体の他に中空でないシリコーンレジン粒子が混在する
ときには、界面活性剤を少量含有する水の中に浸漬して
浮遊物を捕集するとよい。シリコーンレジンの比重は１
より大であるが、中空体になると、見掛け比重が１より
小さくなって水に浮くようになり、かつ、水に界面活性
剤がとけているとシリコーンレジン粒子が水にはじかれ
なくなるからである。シリコーンレジン中空体の中には
熱気流を構成する気体あるいは噴霧時の気体がはいって
いる。したがって、これら気体が空気，窒素ガス，ヘリ
ウムガスの時は、それぞれ空気，窒素ガス，ヘリウムガ
スがはいっている。また、ごく少量の水がはいっている
こともある。水を完全に除去するには３０℃〜１００℃
未満で、かつ、シリコーンレジンの軟化点より低い温度
で加熱すればよい。[0006] Such a silicone resin hollow body is prepared by mechanically mixing or stirring a solution in which a thermoplastic silicone resin is dissolved in a solvent and water to prepare a dispersion, and then spraying the dispersion into a hot air stream. Then, the solvent and water are volatilized and the silicone resin is solidified into hollow particles in a spray state to be easily produced. First, the silicone resin is dissolved in a solvent that dissolves the resin, and the silicone resin forms a uniform solution. The solvent used here can be volatilized in a hot air stream and is incompatible with water. What is necessary is just to select from a soluble and immiscible thing, and the thing whose boiling point is 30-90 degreeC lower than water is desirable. Such solvents include dichloromethane, chloroform, 1,
Examples thereof include 1-dichloroethane, 1,1,1-trichloroethane, acetone, methyl ethyl ketone, and benzene.
Next, the silicone resin solution and water are mixed or stirred to form a dispersion. This can be easily performed by using a blade type high-speed kneader, for example, a pin mixer, a turbulizer, a speed mixer, a Saturn mixer, or the like. The method of spraying into the hot air stream is as follows:
The method is not particularly limited as long as it can spray the solution as fine droplets. Examples of the spraying method include a method in which the dispersion is dropped on a high-speed rotating disk and atomized by centrifugal force to spray the dispersion, a method in which the dispersion is sprayed by injecting the dispersion with gas, and a method in which the dispersion is atomized and sprayed by ultrasonic waves. Although a method is exemplified, it is preferable to use a spray nozzle, which is generally called a two-fluid nozzle, spray the dispersion with a gas, and collide fine particles sprayed from two directions to finer particles. . The spray temperature and the temperature of the hot air flow are usually from room temperature to the boiling point of water, that is, 40 ° C.
It is desirable to be within the range of -90C. Thus, the fine droplets sprayed into the hot air flow, the solvent is volatilized while moving on the hot air flow, hollow silicone resin particles, that is,
It becomes a silicone resin hollow body. Here, during the period from the spraying of the dispersion to the collection, the hot air flow temperature decreases due to the volatilization of the solvent and heat radiation to the outside of the system. It is necessary to adjust the outlet temperature and the air velocity of the stream. When non-hollow silicone resin particles are present in addition to the silicone resin hollow body, it is advisable to collect suspended matters by immersion in water containing a small amount of a surfactant. The specific gravity of silicone resin is 1
Although it is larger, when the hollow body is used, the apparent specific gravity becomes smaller than 1 and the water floats on the water, and when the surfactant is dissolved in the water, the silicone resin particles are not repelled by the water. . A gas constituting a hot air flow or a gas at the time of spraying is contained in the silicone resin hollow body. Therefore, when these gases are air, nitrogen gas, and helium gas, they contain air, nitrogen gas, and helium gas, respectively. It may also contain very little water. 30 ° C to 100 ° C to completely remove water
What is necessary is just to heat at a temperature below and below the softening point of the silicone resin.
【０００７】[0007]
【実施例】次に実施例にて本発明を説明する。実施例
中、部とあるのは重量部を示し、％とあるのは重量％を
示す。Next, the present invention will be described by way of examples. In Examples, "parts" indicates parts by weight, and "%" indicates% by weight.
【０００８】[0008]
【実施例１】メチルシロキサン単位とメチルフェニルシ
ロキサン単位から構成され、そのモル比が１０：９０で
あるメチルフェニルポリシロキサンレジン、すなわち、
シリコーンレジン（軟化点１４０℃，比重１.２５）を
ジクロロメタン（沸点４０℃）に溶解してなるジクロロ
メタン溶液（固形分濃度３０重量％）を１００cc／分、
純水を２５cc／分のフィード量でダイナミックミキサ
（ピンミキサー）内に液送し、回転羽根の回転数２００
０ｒｐｍで混合して分散液とした後、２流体ノズルを使
って、窒素ガスを熱気流としたスプレードライヤー内に
連続的に噴霧した。この時の窒素ガスの熱気流温度は８
０℃、圧は０.５kg／cm2であった。捕集したシリコーン
レジン粒状物を純水１００部と非イオン界面活性剤（ト
リメチルノナノールのエチレンオキサイド付加物）１部
からなる水溶液に２４時間浸漬し、浮遊したシリコーン
レジン中空体を捕集した。シリコーンレジン中空体は平
均粒径が２０μｍであり、外殻の平均厚さが２μｍであ
り、この中空体には窒素ガスの他に空間容積の１％の水
がはいっていた。捕集したシリコーンレジン中空体はシ
リコーンレジン粒状物の７０％であった。沈降した３０
％のシリコーンレジン粒子はカプセルを持たないシリコ
ーンレジン粒子であった。EXAMPLE 1 A methylphenylpolysiloxane resin composed of methylsiloxane units and methylphenylsiloxane units and having a molar ratio of 10:90,
A dichloromethane solution (solid content: 30% by weight) obtained by dissolving silicone resin (softening point: 140 ° C., specific gravity: 1.25) in dichloromethane (boiling point: 40 ° C.) is 100 cc / min.
Pure water is fed into a dynamic mixer (pin mixer) at a feed rate of 25 cc / min.
After mixing at 0 rpm to form a dispersion, the mixture was continuously sprayed into a spray drier using a two-fluid nozzle with a hot gas stream of nitrogen gas. At this time, the hot air flow temperature of nitrogen gas was 8
At 0 ° C., the pressure was 0.5 kg / cm 2 . The collected silicone resin granules were immersed in an aqueous solution consisting of 100 parts of pure water and 1 part of a nonionic surfactant (trimethylnonanol ethylene oxide adduct) for 24 hours to collect floating silicone resin hollow bodies. The hollow silicone resin body had an average particle diameter of 20 μm and an average outer shell thickness of 2 μm. In addition to the nitrogen gas, 1% of the space volume of water was contained in this hollow body. The collected silicone resin hollow body was 70% of the silicone resin granules. Settled 30
% Silicone resin particles were silicone resin particles without capsules.
【０００９】[0009]
【実施例２】メチルシロキサン単位とメチルフェニルシ
ロキサン単位から構成され、そのモル比が２２：７８で
あるメチルフェニルポリシロキサンレジン、すなわち、
シリコーンレジン（軟化点８０℃，比重１.２０）をジ
クロロメタンに溶解してなるジクロロメタン溶液（固形
分３０重量％）を１００cc／分、純水を２５cc／分のフ
ィード量で実施例１で使用したダイナミックミキサに液
送し、回転羽根の回転数１０００ｒｐｍで混合して分散
液とした後、実施例１で使用したスプレードライヤー内
に連続的に噴霧した。この時の窒素ガスの熱気流温度は
７０℃で、圧は０.５kg／cm2であった。捕集したシリコ
ーンレジン粒状物について実施例１と同一の方法で分別
を行い、平均粒径４０μｍであり、外殻の平均厚さが４
μｍであり窒素ガスのはいったシリコーンレジン中空体
を捕集した。捕集したシリコーンレジン中空体はシリコ
ーンレジン粒状物の６０％であった。沈降した４０％の
シリコーンレジン粒子はカプセルを持たないシリコーン
レジン粒子であった。Example 2 A methylphenylpolysiloxane resin composed of methylsiloxane units and methylphenylsiloxane units and having a molar ratio of 22:78,
A dichloromethane solution (solid content 30% by weight) obtained by dissolving a silicone resin (softening point 80 ° C., specific gravity 1.20) in dichloromethane was used in Example 1 at a feed rate of 100 cc / min and pure water at a feed rate of 25 cc / min. The liquid was sent to a dynamic mixer, mixed at a rotation speed of the rotating blades of 1,000 rpm to form a dispersion, and then continuously sprayed into the spray dryer used in Example 1. At this time, the flow temperature of the nitrogen gas was 70 ° C., and the pressure was 0.5 kg / cm 2 . The collected silicone resin particles were fractionated in the same manner as in Example 1 to have an average particle size of 40 μm and an average shell thickness of 4 μm.
The silicone resin hollow body having a thickness of μm and filled with nitrogen gas was collected. The collected silicone resin hollow body was 60% of the silicone resin granules. The settled 40% silicone resin particles were silicone resin particles without capsules.
【００１０】[0010]
【発明の効果】本発明のシリコーンレジン中空体は、平
均粒径が０.１〜１００μｍであるので分散性が良好で
あり、熱可塑性であるのでその軟化点以上の温度で加熱
すると、カプセルが破れて内包していた気体が外部に出
てきて、ゴムスポンジないしゴムフォーム等の発泡源等
となりうるという特徴がある。本発明の製造方法によれ
ば、熱可塑性シリコーンレジン中空体を効率よく製造す
ることができる。The silicone resin hollow body of the present invention has an average particle size of 0.1 to 100 μm and thus has good dispersibility, and is thermoplastic so that when heated at a temperature higher than its softening point, the capsule becomes It is characterized in that the gas that has been torn and contained therein comes out and can be a foaming source such as a rubber sponge or a rubber foam. ADVANTAGE OF THE INVENTION According to the manufacturing method of this invention, a thermoplastic silicone resin hollow body can be manufactured efficiently.
フロントページの続き (72)発明者 浜田 光男 千葉県市原市千種海岸２番２ 東レ・ダウ コーニング・シリコーン株式会社エンジニ アリング部内Continued on the front page (72) Inventor Mitsuo Hamada 2-2 Chikusa Beach, Ichihara City, Chiba Prefecture Dow Corning Silicone Co., Ltd. Engineering Department
Claims (4)
外殻とする平均粒径が０.１〜１００μｍであるシリコ
ーンレジン中空体。1. A hollow silicone resin body having an average particle size of 0.1 to 100 μm using a thermoplastic silicone resin as an outer shell of a capsule.
００℃の範囲内である請求項１記載のシリコーンレジン
中空体。2. The silicone resin has a softening point of 40.degree.
The silicone resin hollow body according to claim 1, which is within a temperature range of 00C.
ンと水との分散液を熱気中に噴霧し、該溶媒と水を揮発
させると共に、噴霧状態で該熱可塑性シリコーンレジン
を中空粒子状に固化させることを特徴とする、請求項１
記載の熱可塑性シリコーンレジン中空体の製造方法。3. A dispersion of a thermoplastic silicone resin dissolved in a solvent and water is sprayed into hot air to volatilize the solvent and water and solidify the thermoplastic silicone resin into hollow particles in a sprayed state. 2. The method of claim 1, wherein
A method for producing the thermoplastic silicone resin hollow body according to the above.
ン粒子を界面活性剤の水溶液に浸漬し、浮遊物を捕集す
ることを特徴とする、請求項１記載のシリコーンレジン
中空体の製造方法。4. The method for producing a hollow silicone resin body according to claim 1, wherein the solidified silicone resin particles according to claim 3 are immersed in an aqueous solution of a surfactant to collect suspended matters.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21052096A JP3921262B2 (en) | 1996-07-22 | 1996-07-22 | Silicone resin hollow body and method for producing the same |
| US08/892,489 US5945043A (en) | 1996-07-22 | 1997-07-14 | Hollow silicone resin particles and method for the preparation thereof |
| EP97305471A EP0820807B2 (en) | 1996-07-22 | 1997-07-22 | Hollow silicone resin particles and method for the preparation thereof |
| DE69704814T DE69704814T3 (en) | 1996-07-22 | 1997-07-22 | Hollow particles of silicone resin and process for their preparation |
| US09/235,210 US6180236B1 (en) | 1996-07-22 | 1999-01-22 | Hollow silicone resin particles and method for the preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21052096A JP3921262B2 (en) | 1996-07-22 | 1996-07-22 | Silicone resin hollow body and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1033971A true JPH1033971A (en) | 1998-02-10 |
| JP3921262B2 JP3921262B2 (en) | 2007-05-30 |
Family
ID=16590736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21052096A Expired - Fee Related JP3921262B2 (en) | 1996-07-22 | 1996-07-22 | Silicone resin hollow body and method for producing the same |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US5945043A (en) |
| EP (1) | EP0820807B2 (en) |
| JP (1) | JP3921262B2 (en) |
| DE (1) | DE69704814T3 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1036544A (en) * | 1996-07-25 | 1998-02-10 | Toray Dow Corning Silicone Co Ltd | Silicone rubber sponge composition and production of silicone rubber sponge |
| JP2001131415A (en) * | 1999-07-19 | 2001-05-15 | Dow Corning Toray Silicone Co Ltd | Silicone rubber sponge-forming composition, silicone rubber sponge and preparation process of silicone rubber sponge |
| JP2007163754A (en) * | 2005-12-13 | 2007-06-28 | Sekisui Chem Co Ltd | Coating agent for antireflection and antireflection film |
| WO2007099814A1 (en) * | 2006-03-02 | 2007-09-07 | Kaneka Corporation | Process for production of hollow silicone fine particles |
| CN113549218A (en) * | 2021-08-06 | 2021-10-26 | 江西新嘉懿新材料有限公司 | Preparation method of hollow spherical silicon resin |
| JPWO2023140263A1 (en) * | 2022-01-21 | 2023-07-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2811590B1 (en) * | 2000-07-17 | 2007-07-13 | Kappa Biotech | HOLLOW POLYMERIC PARTICLE FOR ENCAPSULATION OF SUBSTANCES, METHODS AND AUTOMATED DEVICE FOR MANUFACTURING |
| US7452849B2 (en) * | 2002-07-31 | 2008-11-18 | Dow Corning Corporation | Silicone resin for drilling fluid loss control |
| WO2004013251A1 (en) * | 2002-07-31 | 2004-02-12 | Shell Internationale Research Maatschappij B.V. | Method for drilling a well |
| GB0328236D0 (en) | 2003-12-05 | 2004-01-07 | Dow Corning | Method of making kaolin containing silicone rubber compositions |
| FR2876025B1 (en) * | 2004-10-04 | 2007-02-09 | Oreal | HAIR COSMETIC COMPOSITION BASED ON HOLLOW PARTICLES AND SILICONE FIXING POLYURETHANE |
| FR2876026B1 (en) * | 2004-10-04 | 2007-02-09 | Oreal | HAIR-BASED COSMETIC COMPOSITION BASED ON HOLLOW PARTICLES AND NON-SILICONE FIXING POLYMER |
| CN102430373B (en) * | 2011-09-06 | 2013-11-06 | 哈尔滨工业大学 | Preparation method of organosilicon hollow microsphere |
| DE112016005010T5 (en) * | 2015-10-28 | 2018-09-06 | Sumitomo Electric Industries, Ltd. | An insulated electrical wire and varnish for forming an insulating layer |
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| JPS555787A (en) * | 1978-06-27 | 1980-01-16 | Dow Corning | Method of preparing corpuscular matter containing solid organopolysiloxane |
| JPS63308067A (en) * | 1987-05-21 | 1988-12-15 | ワツカー‐ケミー・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Silicone resin powder and its production |
| JPH0214244A (en) * | 1988-06-30 | 1990-01-18 | Toray Dow Corning Silicone Co Ltd | Thermosetting organopolysiloxane composition |
| JPH0429748A (en) * | 1990-05-24 | 1992-01-31 | Toray Dow Corning Silicone Co Ltd | Preparation of thermally plastic resin fine particles containing catalyst for hydrosilylation reaction |
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-
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- 1997-07-14 US US08/892,489 patent/US5945043A/en not_active Expired - Lifetime
- 1997-07-22 EP EP97305471A patent/EP0820807B2/en not_active Expired - Lifetime
- 1997-07-22 DE DE69704814T patent/DE69704814T3/en not_active Expired - Lifetime
-
1999
- 1999-01-22 US US09/235,210 patent/US6180236B1/en not_active Expired - Lifetime
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| JPS555787A (en) * | 1978-06-27 | 1980-01-16 | Dow Corning | Method of preparing corpuscular matter containing solid organopolysiloxane |
| JPS63308067A (en) * | 1987-05-21 | 1988-12-15 | ワツカー‐ケミー・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Silicone resin powder and its production |
| JPH0214244A (en) * | 1988-06-30 | 1990-01-18 | Toray Dow Corning Silicone Co Ltd | Thermosetting organopolysiloxane composition |
| JPH0429748A (en) * | 1990-05-24 | 1992-01-31 | Toray Dow Corning Silicone Co Ltd | Preparation of thermally plastic resin fine particles containing catalyst for hydrosilylation reaction |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1036544A (en) * | 1996-07-25 | 1998-02-10 | Toray Dow Corning Silicone Co Ltd | Silicone rubber sponge composition and production of silicone rubber sponge |
| JP2001131415A (en) * | 1999-07-19 | 2001-05-15 | Dow Corning Toray Silicone Co Ltd | Silicone rubber sponge-forming composition, silicone rubber sponge and preparation process of silicone rubber sponge |
| JP2007163754A (en) * | 2005-12-13 | 2007-06-28 | Sekisui Chem Co Ltd | Coating agent for antireflection and antireflection film |
| WO2007099814A1 (en) * | 2006-03-02 | 2007-09-07 | Kaneka Corporation | Process for production of hollow silicone fine particles |
| JP5563762B2 (en) * | 2006-03-02 | 2014-07-30 | 株式会社カネカ | Method for producing hollow silicone fine particles |
| CN113549218A (en) * | 2021-08-06 | 2021-10-26 | 江西新嘉懿新材料有限公司 | Preparation method of hollow spherical silicon resin |
| JPWO2023140263A1 (en) * | 2022-01-21 | 2023-07-27 | ||
| WO2023140263A1 (en) * | 2022-01-21 | 2023-07-27 | 松本油脂製薬株式会社 | Thermally expandable microspheres, hollow particles, and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69704814D1 (en) | 2001-06-21 |
| DE69704814T3 (en) | 2006-01-26 |
| EP0820807B1 (en) | 2001-05-16 |
| US6180236B1 (en) | 2001-01-30 |
| DE69704814T2 (en) | 2001-12-06 |
| US5945043A (en) | 1999-08-31 |
| JP3921262B2 (en) | 2007-05-30 |
| EP0820807A1 (en) | 1998-01-28 |
| EP0820807B2 (en) | 2005-08-31 |
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